Quantum geometric spin frustration of antiferromagnetic CuFeO2 enables photocatalytic applications

Xiang Lin Huang, Sz Chian Liou, Meng Yu Kao, Tan Ju Yang, Hsin An Chen, Hsiao Wen Chen, Hsiang Lin Liu, Wei Tin Chen, Guo Jiun Shu*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


Photocatalysis, containing a potential solution to the global crises of energy shortage and the greenhouse effect, has been studied extensively in recent years. The CuFeO2 (abbreviated as CFO) is a material with a Delafossite structure, and has also been widely studied because of its triangular lattice antiferromagnets. The triangular lattice composed of Fe3+ ions, along with strong antiferromagnetic spin coupling between the Fe3+ ions, leads to a geometric spin frustration. Furthermore, CFO is also a potential candidate for the photocatalytic material due to its narrow band gap of 1.1–1.6 eV, electrochemical stability in an aqueous environment, high charge carrier mobility, flat-band potential positioned at ∼ 1 eV, and contains an abundance of raw materials in the earth. In this study, we successfully grew the size and highly-quality CFO single crystals using the optical floating-zone technique. Powder x-ray diffraction (XRD) and Rietveld refinement indicate that the CFO is a rhombohedral structure with a space group of R3̅m, consisting of edge-shared FeO6 octahedron to form the FeO2 layer, and the Cu cations occupied between the two FeO2 layers. The core-level electron energy loss (EEL) spectra found the valence of Fe and Cu in CFO is +3 and +1, respectively. The low-loss EEL spectrum observed two volume plasmons at ∼5 eV and ∼23 eV contributed from the collective oscillation of Cu-O antibonding states σCu−O* and mixed nonbonding Cu 3dxy, σCu−O bonding states, and Fe-O, respectively, based on the density function theory calculation. The optical absorption spectrum measured the energy bandgap for CFO is about 1.5 eV. The Raman spectrum shows significant Eg and A1 g vibration modes corresponding to the in-plane Fe-O and out-of-plane Cu-O vibrations, respectively. Both magnetic susceptibility, χ(T), with the applied magnetic field along the c-axis and specific heat capacity reveal the two magnetic phase transition temperatures at low temperatures: TN1 = 13.5 K when transition from paramagnetic (PM) phase to partially disordered antiferromagnetic, and TN2 = 10.5 K when complete transition from partially disordered antiferromagnetic to antiferromagnetic phase. The additional calculation of magnetic entropy change is 0.15, which is roughly close to 0.2, meaning that only 1/5 of the Fe3+ spins are disordered when transforming from PM states to partially disordered at T < TN1 in this study. The presence of instantaneous ferromagnetic spin arrangement (↑↑↓) extends the residence time of H2O on the surface of CFO, facilitating electron exchange with CFO and promoting photocatalytic water splitting reactions.

Original languageEnglish
Article number172087
JournalJournal of Alloys and Compounds
Publication statusPublished - 2023 Dec 15


  • Delafossite CuFeO
  • Floating-zone method
  • Geometric spin frustration
  • Material properties
  • Photocatalytic material
  • Single crystal

ASJC Scopus subject areas

  • Mechanics of Materials
  • Mechanical Engineering
  • Metals and Alloys
  • Materials Chemistry


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